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1 Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2015 Ligand-free N-arylation of heterocycles using metal-organic framework [Cu(INA) 2 ] as an efficient heterogeneous catalyst Thanh Truong*, Chi V. Nguyen, Ngoc T. Truong, Nam T. S. Phan * Department of Chemical Engineering, HCMC University of Technology, VNU-HCM, 268 Ly Thuong Kiet, District 10, Ho Chi Minh City, Viet Nam * ptsnam@hcmut.edu.vn tvthanh@hcmut.edu.vn Ph: (+84 8) ext Fx: (+84 8) Supporting Information Synthesis of MOFs 1. Cu 3 (BTC) 2 : The procedure to prepare Cu 3 (BTC) 2 was similar to that previously reported [1, 2]. In a typical preparation, a solid mixture of Cu(NO 3 ) 2.3H 2 O (0.438 g, 1.81 mmol) and 1,3,5- benzenetricarboxylic acid (H 3 BTC) (0.236 g, 1.12 mmol) was dissolved in a mixture of DMF (3 ml), ethanol (4 ml) and water (2 ml) in a 20 ml vial. The vial was heated at 85 o C in an isothermal oven for 24 h, yielding light blue crystals. After cooling the vial to room temperature, the solid product was obtained by decanting with mother liquor and washed with DMF (3 x 8 ml). Solvent exchange was then carried out with ethanol (3 x 8 ml) at room temperature. The product was then dried under vacuum at 170 o C for 6 h, yielding g of Cu 3 (BTC) 2 in the form of deep purple crystals (84% based on 1,3,5-benzenetricarboxylic acid). 1

2 Fig S1. X ray powder diffractogram of the Cu 3 (BTC) 2 Fig S2. FT IR spectra of the Cu 3 (BTC) 2 (a) and 1,3,5-benzenetricarboxylic acid (b) 2. Cu 2 (BDC) 2 (BPY): The Cu 2 (BDC) 2 (BPY) was prepared according to literature procedure [3]. A solid mixture of Cu(NO 3 ) 2.3H 2 O (0.105 g, 0.4 mmol), 1,4-benzenedicarboxylic acid (H 2 BDC) (0.068 g, 0.4 mmol), and 4,4 -bipyridine (BPY) (0.062 g, 0.4 mmol) was dissolved in DMF (30 ml). The resulting solution was then distributed in four 20 ml vials. The vials were heated at 120 o C in an isothermal oven for 24 h, yielding light blue crystals. After cooling the vials to room temperature, the solid product was obtained by decanting with mother liquor and washed with DMF (3 x 10 ml). Solvent exchange was then carried out with methanol (3 x 10 ml) at room temperature. The product was then dried under vacuum at 120 o C for 6 h, yielding g of Cu 2 (BDC) 2 (BPY) (75% based on 1,4-benzenedicarboxylic acid). 2

3 Fig S3. X ray powder diffractogram of the Cu 2 (BDC) 2 (BPY) Fig S4. FT IR spectra of the Cu 2 (BDC) 2 (BPY) (a), 4,4 -Bipyridine (b), and 1,4-Benzenedicarboxylic acid (c) 3. Cu 2 (BDC) 2 (DABCO): The Cu 2 (BDC) 2 (DABCO) was prepared according to literature procedures [4, 5-7]. In a typical preparation, a mixture of H 2 BDC (H 2 BDC = 1,4- benzenedicarboxylic acid; g, 3.1 mmol), DABCO (DABCO = 1,4- diazabicyclo[2.2.2]octane; g, 1.67 mmol), and Cu(NO 3 ) 2 3H 2 O (0.8 g, 3.3 mmol) was dissolved in DMF (ml). The mixture was stirred for 2 h, and the resulting solution was then distributed to eight 10 ml vials. The vials were heated at 120 o C in an isothermal oven for 48 h, forming blue crystals. After cooling the vials to room temperature, the solid product was removed by decanting with mother liquor and washed with DMF (3 x 10 ml). Solvent exchange was carried out with methanol (3 x 10 ml) at room temperature. The product was then dried at 140 o C for 6 h under vacuum, yielding 0.57 g of the metal-organic framework Cu 2 (BDC) 2 (DABCO) as light blue crystals (66% based on 1,4-benzenedicarboxylic acid). 3

4 Fig S5. X ray powder diffractogram of the Cu 2 (BDC) 2 (DABCO) Fig S6. FT IR spectra of of 1,4- diazabicyclo[2.2.2]octane (a), 1,4- benzenedicarboxylic acid (b), and the Cu 2 (BDC) 2 (DABCO) (c) 4

5 19.26%. Elemental analysis of the Cu(INA) 2 with ICP - MS indicated an atomic copper about Fig. S7. X-ray powder diffractograms of the Cu(INA) 2 5

6 Fig. S8. SEM micrograph of the Cu(INA) 2. 6

7 Fig. S9. TEM micrograph of the Cu(INA) 2. 7

8 Fig. S10. Nitrogen adsorption/desorption isotherm of the Cu(INA) 2. Adsorption data are shown as tetragons and desorption data as circles 8

9 Fig. S11. Pore size distribution of the Cu(INA) 2 9

10 Fig. S12. TGA analysis of the Cu(INA) 2 10

11 Fig. S13. FT-IR spectra of the Cu(INA) 2 (a) and isonicotinic acid (b) 11

12 Fig S14. 1 H NMR a) and 13 C NMR spectra b) of 1-(4-(1H-pyrazol-1-yl)phenyl)ethanone in CDCl 3 12

13 1-(4-(1H-pyrazol-1-yl)phenyl)ethanone. 4 -iodoacetophenone (492 mg, 2.0 mmol), pyrazole (204 mg, 3 mmol), Cu(INA) 2 (0.03 g, 5 mol%), DMA (4 ml), K 3 PO 4 (848 mg, 2 eq.). After chromatography (ethyl acetate/hexane = 1: 2), 324 mg brown liquid was obtained (87 %). R f = H NMR (500 MHz, CDCl 3, ppm): δ = 8.04 (d, J = 8.5 Hz, 2H), 7.99 (d, J = 2.5 Hz, 1H), 7.79 (d, J = 8.5 Hz, 2H), 7.75 (d, J = 1.5 Hz, 1H), 6.49 (t, J = 4.5 Hz, 1H), 2.60 (s, 3H). 13 C NMR (125 MHz, CDCl 3, ppm): δ = 196.7, 143.3, 142.0, 134.8, 129.9, 126.8, 118.3, 108,

14 Fig S15. 1 H NMR a) and 13 C NMR spectra b) of 1-(4-nitrophenyl)-1H-pyrazole in CDCl 3 14

15 1-(4-nitrophenyl)-1H-pyrazole. 1-iodo-4-nitrobenzene (596 mg, 2.0 mmol), pyrazole (272 mg, 3 mmol), Cu(INA) 2 (0.03 g, 5 mol%), DMA (4 ml), K 3 PO 4 (848 mg, 2 eq.). After chromatography (ethyl acetate/hexane = 1: 4), 328 mg brown liquid was obtained (87 %). R f = H NMR (500 MHz, CDCl 3, ppm): δ = 8.34 (d, J = 9 Hz, 2H), 8.04 (d, J = 2.5 Hz, 1H), 7.89 (d, J = 9 Hz, 2H), 7.8 (s, 1H), 6.52 (s, 1H), 2.60 (s, 3H). 13 C NMR (125 MHz, CDCl 3, ppm): δ = 145.5, 144.4, 142.7, 127.0, 125.3, 118.6, 109, 3. 15

16 Fig S16. 1 H NMR a) and 13 C NMR spectra b) of 1-(4-(1H-pyrrol-1-yl)phenyl)ethanone in CDCl 3 16

17 1-(4-(1H-pyrrol-1-yl)phenyl)ethanone. 4 -iodoacetophenone (592 mg, 2.0 mmol), pyrole (200 mg, 3 mmol), Cu(INA) 2 (0.03 g, 5 mol%), DMA (4 ml), K 3 PO 4 (848 mg, 2 eq.). After chromatography (ethyl acetate/hexane = 1: 4), 307 mg brown liquid was obtained (83 %). R f = H NMR (500 MHz, CDCl 3, ppm): δ = 7.98 (d, J = 8.5 Hz, 2H), 7.41 (d, J = 8.5 Hz, 2H), 7.13 (d, J = 2 Hz, 2H), 6.36 (t, J = 3.5 Hz, 2H), 2.56 (s, 3H). 13 C NMR (125 MHz, CDCl 3, ppm): δ = 196.4, 143.7, 133.8, 129.9, 119.0, 118.8, 111.4, References 1. L. T. L. Nguyen, T. T. Nguyen, K. D. Nguyen, N. T. S. Phan, App. Catal. A 2012, , (2) 2. D. Britt, D. Tranchemontagne, O. M. Yaghi, PNASS 2008, 33, (3) 3. Y. Sakata, S. Furukawa, M. Kondo, K. Hirai, N. Horike, Y. Takashima, H. Uehara, N. Louvain, M. Meiliknov, T. T. Suruoka, S. Isoda, W. Kosaka, O. Sakata, S. Kitagawa, Science 2013, 339, (4) 4. K. Tan, N. Nijem, P. Canepa, Q. Gong, J. Li, T. Thonhauser, Y. J. Chaba, Chem. Mater. 2012, 24, (5) 5. P. Mishra, S. Edubilli, B. Mandal, S. Gumma, Micropor. Mesopor. Mater. 2013, 169, (9) 6. K. Seki, W. Mori, J. Phys. Chem. B 2002, 106, (10) 7. S. Achmann, G. Hagen, M. Hämmerle, I. Malkowsky, C. Kiener, R. Moos, Chem. Eng. Technol. 2010, 33, (11) 17